Polyhaloalkylpolythioalkyl esters and ethers



United States Patent 3,519,672 POLYHALOALKYLPOLYTHIOALKYL ESTERS AND ETHERS Joseph E. Moore, Richmond, Calif., assignor to Chevron Research Company, San Francisco, Calif., a corporation of Delaware N0 Drawing. Continuation-impart of application Ser. No. 414,876, Nov. 30, 1964. This application Oct. 20, 1966, Ser. No. 588,009

Int. Cl. C07c 149/12, 154/00; A01n 9/12 US. Cl. 260-455 8 Claims ABSTRACT OF THE DISCLOSURE Esters and ethers of the formula ROXS R' wherein R represents a polyhaloalkyl group having 1 to 2 carbon atoms and 3 to halogens of atomic number 17 to 35, at least one of said halogens being bonded to the alpha carbon atom, X is alkylene of l to 4 carbon atoms and m is an integer varying from 2 to 3, and R is an organic radical which forms an ester or ether with the remainder of the molecule. Typical R groups are hydrocarbyl, phosphoro, carbonyl, oxycarbonyl, sulfate and sufonate groups. These esters and ethers are useful as fungicides.

This application is a continuation-in-part of application Ser. No. 414,876, filed Nov. 30, 1964, now abandoned.

This invention relates to novel esters and ethers which contain a polyhalo(lower)alkylpolythioalkyl group and their use as fungicides.

The compounds of this invention may be represented by the general formula:

ROXS R' where R represents a polyhaloalkyl group having 1 to 2 carbon atoms and 3 to 5 halogens of atomic number 17 to 35, at least one of said halogens being bonded to the alpha carbon atom, X is alkylene of 1 to 4 carbon atoms, m is an integer varying from 2 to 3, and R is an organic radical which combined with OXS R' forms an ether or ester. Halogens of atomic number 17 to 35 are chlorine and bromine. The alpha carbon atom of the polyhaloalkyl group is bonded to a sulfur of the polysulfide (S group.

X is an alkylene group of from 1 to 4 carbons, e.g., methylene, ethylene, trimethylene, tetramethylene, isopropylene, 1,3-butylene, etc. The RO group is bonded to a primary carbon, that is, the carbon bonded to oxygen has two hydrogens. Preferred alkylene groups contain 2 to 3 carbons.

The esters and ethers of this invention may be con sidered to be derivatives of alcohols. Thus, in a broad sense R is an or anic radical which forms a bond with oxygen and may be cleaved on hydrolysis to regenerate the alcohol as follows:

The R groups do not contribute significantly to the biological activity of the compounds of this invention. However, they may provide a means for'special application. or more attractive physical properties, e.g., hydrophobic, lipophilic, etc.

The R groups which form esters or ethers with OXS R' contain 1 to about 12 carbon atoms. Included among such groups are aliphatic and aromatic hydrocarbyl groups such as alkyl, alkenyl and phenyl, carbacyl, carbamoyl, 0,0-dialkyl phosphoro, alkoxycar- 3,519,672 Patented July 7, 1970 bony], thioalkoxycarbonyl, sulfate, sulfonate, borate and the like.

Among preferred R groups are the following:

u C R2 where R is a halohydrocarbyl group having 0 to 1 halogens of atomic number 17 to 35 and l to about 8 carbon atoms or a halohydrocarbylamino group having 0 to 1 halogen of atomic number 17 to 35 and 1 to about 8 carbon atoms,

where Y is a chalcogen atom of atomic number 8 to 16, i.e., O and S, and R is a halohydrocarbyl group having 0 to 1 halogen of atomic number 17 to 35 and 1 to about 8 carbon atoms or halophenythioalkyl in which the halogen is of atomic number 17 to 35,

where R is a hydrocarbyl group of 1 to about 6 carbon atoms,

(l) O ll where R is OXS R' as defined above,

Examples of radicals which R may represent are alkyl such as methyl, ethyl, hexyl and octyl, butenyl, phenyl, benzyl, tolyl; haloalkyl such as chloromethyl, chloroethyl, bromopropyl and chloroamyl, chloropropenyl, bromophenyl, chlorobenzyl, 4 chloro-6-inethylphenyl; alkylamino such as methylamino, ethylamino, butylamino, hexylamino and chlorobutylamino, chlorophenylamino, bromophenylamino, 6 bromo-2-methyl-phenylamino and the like.

Examples of specific groups which R may be are methyl, ethyl, isopropyl, hexyl, octyl, chloroethyl, chloropropyl, bromoamyl, chlorophenyl, bromobenzyl, chlorobutenyl, 6-chloro-2-methylphenyl, chlorophenylthioethyl, bromophenylthiopropyl, chlorophenylthiobutyl and the like.

Examples of R are methyl, ethyl, propyl, hexyl, propargyl, butenyl and phenyl.

Illustrative of the novel compounds of this invention are the following compounds:

' -(1,1,2,2-tetrachloroethyldithio)propyl S-ethyl thiolcarbonate; 'yperchloroethyltrithio propyl hexanoate; di-[B-(1,2,2-trich1oroethyldithio)ethyl] sulfate; di- [B-( 1,2,2,Z-tetrachloroethyldithio)ethyl] sulfate; ethyl ,8- 1,1,2-trichloroethyldithio)ethyl sulfate; butyl 'y-(l-chl0r0-2,2-dibrom0ethyl)dithio propyl sulfate; di [5- (trichloromethyldithio )ethyl] sulfite; di['y-(1,1,2,2-tetrachloroethyldithio)propyl]sulfite;

3 0,0-dimethyl O-[[3-(perchloroethyldithio)ethyl] phosthe methods of preparation of the novel compounds of phate; this invention: 0,0-diprpyl O-[fl-(1,2,Z-trichloroethyldithio)ethyl] EXAMPLE I phosphate; 0,0-di-phenyl O-[p-(1,l,2,2-tetrachloroethyldithio) A solution of 5.6 grams of 4-chlorophenylisocyanate,

ethyl]phosphate; 5 10.0 grams of 2-hydroxyethyl 1,2,2,2-tetrachloroethyl di- 0,0-dirnethyl O-[fl-(perchloroethyldithio)propyl] sulfide, and one drop of dibutyl tin dilaurate in 50 mls. P p of dry benzene were allowed to stand for one week at methyl-p-(trichloromethyldithio)ethyl ether; room temperature. The solvent was removed by distillaethyl-'y-(l,l,2,2-tetrachloroethyltrithio)propyl ether; tion, the product being heated to a maximum temperature amyl-y-(perchloroethyldithio)propyl ether; and of 100 C. at 0.4 mm. Twelve grams of 4-chlorophenylhexyl-p-(tribromomethyldithio)propyl ether. carbamoyloxyethyl-l,2,2,2-tetrachloroethyl disulfide was y din Applicants novel compounds may be prepared accord obtained as an oil which slowly crystallized on stan ing to general methods known in the art. The esters may Analysls-Theory (P t): N, 3.3. Found (percent). be prepared by condensing an appropriate w-polyhaloalkylpolythio alkanol with an appropriate acid. Acidic EXAMPLE H compounds such as acids, acid anhydrides, and acid halides may be used according to procedures known in Into a flask fitted with condenser, thermometer, stirrer, the art. When desirable, transesterification may also be and dropping funnel was introduced 8.5 grams of 1,1,2,2- used. Etherification may be achieved with sulfate esters, tetrachloroethylsulfenyl chloride in 100 ml. carbon tetraactive halogen compounds and the alkoxide of the w-polychloride. Into the mixture cooled in an ice bath was added haloalkylpolythio alcohol by methods known in the art. 3.3 grams of a 61% solution of Z-methoxyethyl mercap- For making some of the compounds it may be preferable tan diluted with carbon tetrachloride. The mercaptan was to prepare the oxygen derivative first and then contact added dropwise and very slowly. After addition was comthe resulting mercaptan with the desired polyhaloalkylthio pleted, the reaction mixture was refluxed for about 10 or thiosulfenyl halide. minutes. The mixture was then allowed to cool to room The alcohol precursors of the compounds of this intemperature and the solvent stripped under a water vention may be prepared by reacting a mercapto alcohol vacuum. The residue was distilled yielding 4 grams of with a polyhaloalkylsulfenyl or -thiosulfenyl halide. Ternmethyl-541,1,2,2-tetrachloroethyldithio)ethyl ether boilperatures in the range of 0 to 50 C. may be used, but ing in a range of 100 to 117 C. at 0.4 to 0.6 mm. ambient temperatures or somewhat lower are preferred, mercury. that is, temperatures in the range of 0 to 25 C. Various Analysis.Theory (percent): Cl, 48.8; S, 22.1. Found solvents may be used in the reaction which are inert to (percent): Cl, 46.4; S, 23.7. the reactants and products. Preferred solvents are halo- The following table, Table I, lists other compounds of genated hydrocarbons. this invention which were prepared according to general The following examples are ofiered as illustrative of procedures knowninthe art.

TABLE I 01 S N or P Structure Cale. Fd. one. Fd. 0310. Ed.

I 0o1 -s-s-oH,0H20doH3- 39.4 34.3

CCI3-S'S S'OH2CH2ONHCH3 4 4(N)3 s CHCla-CHCl-SSCHaCHz-OCNHO1 35.8 36.2 3 5 N 3 5 GHOh-OHCl-SS-CHg-CHz0--l. (OOzH) 28.1 28.9 17.0 19.0

l CCl3CHCl-sSCH5CH10C-0CH2OHr-sl 36.2 36.8 19.7 19.9

oOl -CHCi-SsoH,CHiogs-0,H5 38.8 41.0 26.4 25.5

CClaCHC1-S--S HzCHz0CNH-Cl 58-63 3.4(N)4,1

COl OHCI-S--SCH1CHr-O- -NHCH 42.5 40.3 19.3 18.6

co1.OHC1s--s--0H2--0H4-1 (00mm 34.4 35.9 15.5 17.1 7.5(I)6.3

TABLE I-Continued 01 S Nor]? Structure c010. Fd. c010. Fd. c010. Fd.

i GC1 -CHCl-S-SCHCH4OCNH ..5s- 35.0 35.0 10.2 10.0

1 oon-onoi-s-s43114-0124'1o(i01 401. 50.3 40.0 13.2 20.2

1 CHCl -CClSSCH4-CH4OGCH1 44.0 43.3 20.1 20.5

1 anon-con-s-scH,cH10 i-0 JH2cH4s01 30.2 35.0 10.7 20.0

1 each-cows-s-om-cmo-bsol 30.0 34.0 21.5 23.3

ll CHClg-CClaSSCHrCH2O-C-SC2H5 38.8 43.2 22.4 26.4

f CHCl -CCl -SS-CHz-CHOCNH@CI 41.3 30.2 14.0 15.0 3.3(N)3.1

i1 CHCl -CCl SSCHz-CH20CNH 41.3 30.1 14.0 15.1

i CHCl -CCh-S-S-CH4CHz-0-ONHOH5 42.5 40.1 10.3 10.0

0 anon-oon-s-s-orn-cm-ops 40.2 50.0 20.1 25.0

01100-0e12-s-s-oH4-0H40 1s 0 47.5 45.3 20.3 20.7

3 J CHClz-CCl2S-S-CH2-CH2OP(OC2H5)2 7.5 (II)5.7

5 1 CHC14CCl2S-SCH2CHzOfiOCiH5 30.3 40.7 25.0 25.4

CHCl -CC1;S-SOH4CH40-CH The novel compounds of this invention were tested for fungicidal activity against Pythium ultimum and Rhizoctonia solani by means of the mycelial drop test. This test is designed to measure the fungitoxic activity of fungicidal chemicals in terms of their degree of inhibiton upon mycelial growth.

Each fungitoxic compound to be tested was dissolved in acetone in dilutions as indicated in the following table. Paper discs previously inoculated by impregnation with equal amounts of a particular fungus mycelium and placed on potato dextrose agar medium were treated by applying a precise and equal volume of each of these fungicidal solutions to their center. Following treatment with the fungitoxic chemical, the discs were incubated along with inoculated but untreated control discs at ambient temperatures until such time as these untreated control discs were filled with mycelial growth. Activity of the fungitoxic chemical tested was determined by comparative measurements of radii of mycelial growth away from the edge of the disc in treated and untreated samples. From this comparison a percentage inhibition of growth area can be determined. The results are tabulated in columns I and II of Table II.

The novel compounds of this invention were also compared for fungicidal activity by means of The Standard Spore Slide-Germination Method for Determining Fungicidal Activity. The results obtained are expressed in terms of percent inhibition of germination of fungus spores.

Each compound to be tested was dissolved in acetone in dilutions to the desired concentration. These solutions were then pipetted into the wells of depression slides and allowed to dry. The wells were filled with a spore suspension of the test organism, Monilinia fructicola, and incubated in a moist chamber overnight. A group of one hundred spores was examined and the number of spores germinated and not germinated was counted and recorded to show the biological activity in terms of the percentage germination inhibition.

The results of these tests for various chemicals of this invention on the particular fungus mycelium and spores are indicated as shown in column III of Table II.

Further, these compounds may not only be applied alone or in mixes with other compounds of the disclosed class, but may also be used in combination with other active toxicants in the formulation of fungicidal compositions.

The compounds may be applied to any environmental area which is a host to fungus or susceptible to fungus attack. For example, the fungicidal compositions may be sprayed or otherwise applied directly to a plant or other host, may be applied to the plant seed, sprayed upon the soil or other plant environment, or used in similar ways TABLE II I II III Structure Pythium Rhizoctonia Monilinia P.p.m. Percent P.p.m. Percent P.p.m. Percent or or o I I II 500 100 500 100 100 HCC-SSCHQCHQO -CH1 250 100 250 100 3 100 125 100 150 72 1 100 01 01 I I II 500 100 500 10 100 Lt- 3-c :s-s-o1no1-r2oo0o1n-o1r:s o1 250 so s 62 I I II 1,000 29 1, 000 9 10 100 H-(|3C|}S-S-OH2OH2OCS -01 3 I II 1, 000 100 1, 000 100 10 100 H-C-CS-S-CH2CH20-CS- CH2CH3 500 100 500 as 3 100 250 100 250 40 c1 c1 I I II 500 100 500 100 10 100 HC-CS-SCH CHzOCNH -01 250 100 250 as 3 100 1 I 125 11 1 4s oi or I II 10 100 11-( 3-( 3-s-s-oH2oH20CNH 3 94 I I II 500 100 500 100 10 100 H-(JC--SSOHg0H 0C-NHCII3 250 100 250 100 a 100 125 100 125 86 1 100 01 or 01 G1 0 1 500 100 500 94 10 100 HC-- -SSCH2OHO -s 250 100 250 as a 100 125 100 125 22 1 or 2 0 II 10 100 n-o-o-s-s-omomo s 1,000 100 1,000 91 a 1 I I T/ 500 100 500 so 10 100 H(]3-(|1S-SCI-IOHOP\ 250 79 250 3 100 c1 or 001115 I" I? H(IJC-SS-CHQCHzO- s -OC2H5- 1, 000 100 1, 000 100 10 100 1, 000 100 1, 000 1, 000 10 100 H--COSSCHzCHzO-CH3.-- so 100 500 78 other solvents, dispersing agents, or emulsifying agents.

so as to effect the control of fungus and fungus caused diseases.

I claim:

1. Compounds having the formula ROXS R' where R represents a polyhaloalkyl group having 1 to 2 carbon atoms and 3 to 5 halogen atoms of atomic number 17 to 35, at least one of said halogens being bonded to the alpha carbon atom, X is alkylene of 1 to 4 carbon atoms, m is in integer varying from 2 to 3 and R is (a) -(ilR where R contains 1 to about 8 carbon atoms and is hydrocarbyl, monohalohydrocarbyl in which the halogen is of atomic number 17 to 35, hydrocarbylamino or halohydrocarbylamino in which the halogen is of atomic number 17 to 35 or O (b) i iYR where Y is a chalcogen atom of atomic number 8 to 16 and R is hydrocarbyl of 1 to about 8 carbon atoms, monohalohydrocarbyl of 1 to about 8 carbon atoms, in which the halogen is of atomic number 17 to 35 or halophenylthioalkyl in which the halogen is of atomic number 17 to 35 and the alkyl group contains 1 to about carbon atoms. 2. The compounds of claim 1 Where m is 2. 3. The compounds of claim 1 where R is 1,1,2,2,- tetrachloroethyl.

4. The compounds of claim 1 wherein R is trichloromethyl.

5. The compounds of claim 1 where R is O I! C-R2 and R is alkyl, alkylamino, phenylamino, halophenylamino or haloalkyl.

6. The compounds of claim 1 weherin R is and Y is a chalcogen atom of atomic number 8 to 16 and R is alkyl, chlorophenyl or chlorophenylthioalkyl in which the alkyl group contains 1 to about 5 carbon atoms.

7. The compounds of claim 1 wherein R is and R contains 1 to about 8 carbon atoms and is alkyl, alkenyl, aryl, monochloroalkyl, monochloroaryl, alkylamino, arylamino, monochloroalkylamino or monochloroarylamino.

8. The compounds of claim 1 wherein R is and Y is a chalcogen atom of atomic number 8 to 16 and R is alkyl, monochloroalkyl, monochloroaryl or monochlorophenylthioalkyl in which the alkyl contains 1 to about 5 carbon atoms.

References Cited CHARLES B. PARKER, Primary Examiner D. R. PHILLIPS, Assistant Examiner US. Cl. X.R. 

